Chiral Overpass-Induction in Dynamic Helical Polymers Bearing Pendant Groups with Two Chiral Centers.
摘要:
The dynamic behaviour of helical polymers bearing pendants with two chiral centers was studied. Controlled conformational changes at the chiral units placed either closer or further to the main chain promote different helical structures. Although the first residue is usually responsible for commanding a specific helicity (P or M), herein it was found that the second chiral center is also able to induce a preferred helical sense when is located spatially closer to the main chain, thereby cancelling the order from the first chiral moiety. This result is achieved through proper coordination with a metal cation. As proof of concept, PPAs that bear one and two chiral amino acid units of different sizes and configuration combinations (L/D alanine and L/D phenylalanine) as pendants were evaluated. In total, ten polymers were studied. This result constitutes the first report of axial control from the remote stereocenter in polymers bearing complex stereopendants.
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DOI:
10.1002/anie.201915213
年份:
2019
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